CN116654948A - W-B powder material and preparation method thereof - Google Patents

W-B powder material and preparation method thereof Download PDF

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CN116654948A
CN116654948A CN202310669168.0A CN202310669168A CN116654948A CN 116654948 A CN116654948 A CN 116654948A CN 202310669168 A CN202310669168 A CN 202310669168A CN 116654948 A CN116654948 A CN 116654948A
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powder
phase
powder material
sintered
sintering
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CN116654948B (en
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李军
刘颖
黄伟
王仁全
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P10/25—Process efficiency

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Abstract

The invention relates to the technical field of metal boride, and particularly discloses a W-B powder material and a preparation method thereof. The preparation method of the W-B powder material comprises the steps of proportioning W powder and B powder, ball milling, adding bridging agent polyethylene glycol, mixing, pre-sintering to remove polyethylene glycol after uniform mixing, and sintering at a low temperature of 1000-1200 ℃ to obtain the pure-phase W-B powder material. The invention realizes the mechanical interlocking of the W powder and the B powder by utilizing the bridging action of the polyethylene glycol on the W powder and the B powder and the mechanical force of ball milling, greatly shortens the diffusion distance between W, B atoms in the solid phase synthesis reaction process, can synthesize the pure phase W-B compound by short-time sintering at the low temperature of below 1200 ℃, has simple process and low manufacturing cost, can accurately regulate and control the phase of the product, and is suitable for mass industrialized production.

Description

W-B powder material and preparation method thereof
Technical Field
The invention belongs to the technical field of metal boride, and particularly relates to a W-B powder material and a preparation method thereof.
Background
The tungsten-boron (W-B) binary compound mainly comprises W 2 B、WB、WB 2 、W 2 B 5 、WB 4 And WB 12 And the W-B binary compound has high boron content, tungsten content and density, so that the W-B binary compound has the shielding function of thermal neutrons and gamma raysThe W-B binary compound has good wear resistance, corrosion resistance and chemical stability, and researches show that the W-B binary compound has wide industrial application prospects in the fields of nuclear radiation shielding, wear resistance and the like.
At present, there are few reports about the synthesis method of W-B binary system compounds at home and abroad, and the university of northeast ("high temperature solid phase reaction for synthesizing tungsten boride powder", cao Xiaozhou, etc.; rare metal materials and engineering, 43, 8 th, 2014, 8 th) uses boron and tungsten as raw materials to prepare tungsten boride powder by adopting a high temperature solid phase synthesis method, and the reaction between B powder and W powder is a solid phase sintering reaction, so that the synthesis of WB with higher purity is required 2 It is necessary to raise the sintering temperature and, at the same time, since B has a volatilization loss at high temperature, when the molar ratio of B/W is 2.5, after isothermal sintering treatment is carried out for 1 hour at 1400 ℃ or more, WB with higher purity can be formed 2 . The patent document of application number 201710423117.4 discloses a neutron and gamma-ray comprehensive shielding filler and a preparation method thereof, which also adopts a solid phase synthesis method to prepare a pure phase W by mixing materials and materials according to W, B atomic ratio of 2:1, sintering for 4h at 1350 ℃, and reacting and synthesizing 2 B sintered body, W to be prepared 2 B crushing the sintered body to obtain W 2 B powder, it can be seen that the preparation of pure phase W-B powder in the patent document has the defect of higher synthesis temperature.
Therefore, it is desirable to provide a method for preparing a W-B-based powder material, which can improve the defect that the solid phase synthesis reaction of W, B to form a pure-phase W-B compound needs to be sintered at high temperature.
Disclosure of Invention
The invention aims to provide a W-B powder material and a preparation method thereof, which can overcome the defect that a pure-phase W-B compound formed by W, B solid phase synthesis reaction needs to be sintered at high temperature.
In a first aspect, the present invention provides a method for preparing a W-B-based powder material, comprising the steps of:
s1, proportioning: weighing W powder and B powder according to a proportion as raw material powder, wherein the average particle size ratio of the W powder to the B powder in the raw material powder is 0.1-35 mu m: 0.1-30 mu m, weighing 1-3% of polyethylene glycol according to the mass percentage of the raw material powder, wherein the average molecular weight of the polyethylene glycol is 6000-12000;
s2, ball milling: ball milling and mixing the raw material powder and polyethylene glycol, and uniformly mixing to obtain mixed powder;
s3, presintering: the mixed powder is placed under the temperature condition of 250 ℃ to 650 ℃ for heat treatment for 1 to 8 hours, and presintered powder is obtained;
s4, sintering: sintering the presintered powder for 2-5 hours at the temperature of 1000-1200 ℃ to obtain sintered powder;
s5, crushing: and crushing the sintered powder to obtain the W-B powder material.
Optionally, in step S1, W powder and B powder are weighed as raw material powders according to an atomic weight ratio W: b=1 (0.5 to 2.7).
Optionally, in step S2, wet milling is adopted, and the ball-to-material ratio of the wet milling is 2-10: 1, the ball milling rotating speed is 100-500 rpm, and the ball milling time is 5-30 h.
Optionally, in step S1, W powder and B powder are weighed as raw material powders according to an atomic weight ratio W: b=1 (1 to 1.2).
Optionally, in step S4, the pre-sintered powder is sintered for 2-5 hours at the temperature of 1000-1100 ℃ to obtain the sintered powder.
Optionally, in step S1, the W powder and the B powder are weighed as raw material powders according to an atomic weight ratio W: b=2 (5 to 5.3).
Optionally, in step S1, W powder and B powder are weighed as raw material powders according to an atomic weight ratio W: b=2 (1.1 to 1.3).
Optionally, in step S4, the pre-sintered powder is sintered for 2-5 hours at 1100-1200 ℃ to obtain sintered powder.
In a second aspect, the present invention provides a W-B-based powder material obtained by the method for producing a W-B-based powder material.
Optionally, the phase structure of the W-B powder material is WB phase and W phase 2 B phase or W 2 B 5 One of the phases.
In summary, the invention has at least one of the following beneficial effects:
1. the invention provides a preparation method of a W-B powder material, which realizes the mechanical interlocking of W powder and B powder by utilizing the bridging action of polyethylene glycol on the W powder and the B powder and the mechanical force of ball milling, greatly shortens the diffusion distance between W, B atoms in the solid phase synthesis reaction process, can sinter and synthesize a pure-phase W-B compound in a short time under the low temperature condition of below 1200 ℃, has simple process and low manufacturing cost, can accurately regulate the phase of a product, and is suitable for mass industrialized production.
2. The invention provides a W-B powder material, which has a pure phase W-B compound structure, wherein the phase structure of the W-B powder material is WB phase and W phase 2 B phase or W 2 B 5 One of the phases.
Drawings
FIG. 1 is an XRD pattern of the pre-sintered powder of example 1;
fig. 2 is an SEM image of the pre-sintered powder of example 1;
FIG. 3 is an XRD pattern of the W-B powder material of example 1;
FIG. 4 is an SEM image of a W-B powder material of example 1;
FIG. 5 is an XRD pattern of the W-B powder material of example 2;
FIG. 6 is an SEM image of a W-B powder material of example 2;
FIG. 7 is an XRD pattern of the W-B powder material of example 3;
FIG. 8 is an SEM image of a W-B powder material of example 3;
FIG. 9 is an XRD pattern of the W-B powder material of example 4;
FIG. 10 is an SEM image of a W-B powder material of example 4;
FIG. 11 is an XRD pattern of the W-B powder material of example 5;
FIG. 12 is an XRD pattern of the W-B powder material of comparative example 1;
FIG. 13 is an XRD pattern of the W-B powder material of comparative example 2;
FIG. 14 is an XRD pattern of the W-B system powder material of comparative example 3;
FIG. 15 is an XRD pattern of the W-B system powder material of comparative example 4;
FIG. 16 is an XRD pattern of the W-B powder material of comparative example 5;
FIG. 17 is an XRD pattern of the W-B system powder material of comparative example 6;
FIG. 18 is an XRD pattern of the W-B powder materials of comparative example 7 and example 1;
fig. 19 is an XRD pattern of the W-B-based powder material of comparative example 8 and example 2.
Detailed Description
The invention provides a W-B powder material and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to prepare the W-B system powder material, the current research mostly adopts high-temperature solid phase reaction, the high-purity W powder and the high-purity B powder are mixed, subjected to reaction sintering, and subjected to heat preservation and sintering at a temperature of more than 1300 ℃, so that a pure-phase W-B system sintered body can be prepared, and the sintered body is crushed to prepare the W-B system powder material. However, the sintering temperature is too high, so that the preparation energy consumption is large, and the burning loss of the B powder at high temperature is large, resulting in the increase of the preparation cost of the W-B powder material. In order to overcome the technical defects in the related art, the inventor surprisingly found through long-time research that polyethylene glycol is added in the ball milling process of W powder and B powder, the polyethylene glycol can play a bridging role between the W powder and the B powder, and the mechanical interlocking of the W powder and the B powder is further realized by combining the acting force of a ball milling medium in the ball milling process, so that the diffusion distance between the W powder and the B powder in the solid phase reaction process can be effectively shortened, the sintering temperature in the subsequent solid phase sintering process can be reduced, the process cost of the prepared W-B powder material can be greatly reduced by performing short-time sintering at the low temperature of 1200 ℃, and the phase structure of the prepared pure-phase W-B powder material can be accurately regulated and controlled according to the target product. Further, the inventors found that the ratio of the particle diameters of the W powder and the B powder, the addition amount of polyethylene glycol, and the molecular weight have a significant influence on bridging action of the W powder and the B powder in the course of the study, and that the ratio of the average particle diameters of the W powder and the B powder is 0.1 to 35 μm: the addition amount of the polyethylene glycol is 1 to 3 weight percent of the raw material powder, and the average molecular weight of the polyethylene glycol is 6000 to 12000, thus being beneficial to preparing the pure phase W-B compound by sintering under the low temperature condition.
Specifically, the invention provides a preparation method of a W-B powder material, which comprises the following preparation steps:
s1, proportioning: weighing W powder and B powder according to a proportion as raw material powder, wherein the average particle size ratio of the W powder to the B powder in the raw material powder is 0.1-35 mu m: 0.1-30 mu m, weighing 1-3% of polyethylene glycol according to the mass percentage of the raw material powder, wherein the average molecular weight of the polyethylene glycol is 6000-12000;
s2, ball milling: ball milling and mixing the raw material powder and polyethylene glycol, and uniformly mixing to obtain mixed powder;
s3, presintering: the mixed powder is placed under the temperature condition of 250 ℃ to 650 ℃ for heat treatment for 1 to 8 hours, and presintered powder is obtained;
s4, sintering: sintering the presintered powder for 2-5 hours at the temperature of 1000-1200 ℃ to obtain sintered powder;
s5, crushing: and crushing the sintered powder to obtain the W-B powder material.
In some embodiments of the present invention, in step S1, W powder and B powder are weighed as raw material powders at an atomic ratio W: b=1 (0.5 to 2.7).
In some embodiments of the present invention, in step S2, wet milling is used, and the weight ratio of the ball material of the wet milling is 2-10: 1, preferably 3 to 8:1, a step of; the ball milling speed is 100-500 rpm, preferably 100-300 rpm, and more preferably 150-240 rpm; the ball milling time is 5-30 h, preferably 10-25 h; the solvent for wet milling is absolute ethyl alcohol, isopropanol or acetone, preferably absolute ethyl alcohol; the volume ratio of the material to the grinding balls to the solvent is 1:1-6, preferably 1:1-3. The polyethylene glycol plays a bridging role on the W powder and the B powder in the ball milling process, and the technological parameters of ball milling are controlled, so that the W powder and the B powder are uniformly mixed, the bridging role of the polyethylene glycol is fully exerted, and the mechanical interlocking between the W powder and the B powder is realized by utilizing the mechanical force of ball milling.
In some embodiments of the present invention, in step S1, the ratio of the average particle diameters of the W powder and the B powder in the raw material powder is preferably 0.1 to 20 μm:0.1 to 20. Mu.m, more preferably 0.5 to 10. Mu.m: 3-15 mu m. By controlling the particle size ratio of the W powder to the B powder, the good dispersion and bridging of the W powder and the B powder are realized, the mutual diffusion distance between W, B atoms in the subsequent solid phase synthesis reaction process is shortened, and the formation of a pure phase W-B compound is promoted.
In some embodiments of the invention, in step S1, the average molecular weight of the polyethylene glycol is preferably 8000 to 11000. By controlling the molecular weight of polyethylene glycol, the polyethylene glycol can exert the bridging effect on the W powder and the B powder to the maximum extent, and simultaneously, the polyethylene glycol can be removed in the presintering process to obtain the pure W-B compound.
In some embodiments of the present invention, in step S3, the mixed powder is sintered under vacuum or inert atmosphere, the vacuum degree is 10 ╳ 10 -1 Pa or less, preferably 6 ╳ 10 -1 Pa or less; the heat treatment process is preferably carried out at 250-600 ℃ for 2-5 hours, and more preferably 500-600 ℃ for 2-4 hours, so as to obtain the presintered powder. By controlling the pre-sintering process parameters, the polyethylene glycol is removed, W, B powder is activated, and solid phase synthesis reaction between the subsequently sintered W, B powder is promoted. For facilitating the subsequent sintering, the pre-sintered powder prepared by the pre-sintering is preferably slightly ground into powder particles in a mortar and then sintered.
In some embodiments of the present invention, in step S4, the pre-sintered powder is sintered under vacuum or inert atmosphere, the vacuum degree is 10 ╳ 10 -2 Pa or less, preferably 10 ╳ 10 -3 Pa or below. The pure W-B compound can be prepared by controlling the sintering atmosphere.
In some embodiments of the present invention, the raw material powder is formulated according to the target product, and in step S1, when the target product is WB, the raw material powder is formulated according to the atomic ratio W: b=1 (1 to 1.2),weighing W powder and B powder as raw material powder; correspondingly, in the step S4, the presintered powder is sintered for 2 to 5 hours at the temperature of 1000 to 1100 ℃, preferably 1030 to 1080 ℃ for 2 to 4 hours. The target product is W 2 When B, according to the atomic ratio W, B=2, (1.1-1.3), weighing W powder and B powder as raw material powder; correspondingly, in the step S4, the presintered powder is sintered for 2 to 5 hours at the temperature of 1100 to 1200 ℃, preferably 1130 to 1180 ℃ for 2 to 4 hours. The target product is W 2 B 5 In the step S4, the pre-sintered powder is sintered for 2 to 5 hours at 1100 to 1200 ℃, preferably 1130 to 1180 ℃ for 2 to 4 hours. The single-phase W-B compound powder material is prepared by controlling the proportion of the raw materials and the sintering process, and the powder material with fine and uniform particles is prepared.
In some embodiments of the present invention, in step S5, the sintered powder is crushed by ball milling to prepare the W-B-based powder material. Preferably, wet milling is adopted for ball milling, and the weight ratio of the ball materials of the wet milling is 2-10: 1, preferably 3 to 8:1, a step of; the ball milling speed is 100-500 rpm, preferably 100-300 rpm, and more preferably 150-240 rpm; ball milling time is 5-10 h; the solvent for wet milling is absolute ethyl alcohol, isopropanol or acetone, preferably absolute ethyl alcohol; the volume ratio of the material to the grinding balls to the solvent is 1:1-6, preferably 1:1-3.
The phase structure of the W-B powder material prepared by the invention is WB phase and W 2 B phase or W 2 B 5 One of the phases is a pure phase powder material of a single phase, the particles of the powder material are fine and uniform, the average particle size of the WB powder material is 1-5 mu m, the purity of the powder material is high, and the true density is more than 98.9% of the theoretical density.
The invention will now be described in detail with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
In the following examples, the purity of the W powder and the B powder was 99.95% or more.
Example 1
The preparation method of the W-B powder material comprises the following preparation steps:
s1, proportioning: weighing W powder and B powder as raw material powder according to an atomic weight ratio W:B=1:1.1, wherein the average particle size ratio of the W powder to the B powder in the raw material powder is 0.5 mu m:5 μm, and weighing 2% of polyethylene glycol according to the mass percentage of the raw material powder, wherein the average molecular weight of the polyethylene glycol is 10000 (PEG 10000, CAS 25322-68-3).
S2, ball milling: mixing raw material powder and polyethylene glycol by ball milling, wherein the ball milling adopts a polyurethane ball milling tank and stainless steel grinding balls, and the weight ratio of ball materials is 6: and 1, wet milling is carried out by taking absolute ethyl alcohol as a solvent, the volume ratio of the materials to the grinding balls to the absolute ethyl alcohol is 1:1.2, the ball milling rotating speed is 200rpm, and after ball milling is carried out for 24 hours, the mixture is taken out and dried, so as to obtain mixed powder.
S3, presintering: placing the mixed powder into a vacuum sintering furnace, and vacuumizing to 6 ╳ 10 -1 Pa, heating to 600 ℃ at a speed of 8 ℃/min, heat-preserving, performing heat treatment for 3 hours, stopping heating, cooling, taking out to obtain presintered powder, and slightly grinding the presintered powder in a mortar to disperse the partially agglomerated blocks into powder particles. Fig. 1 is an XRD pattern of pre-sintered powder particles, and only the elemental W phase is detected and no other phases are detected in fig. 1, indicating that no solid phase reaction occurs between the W powder and the B powder during ball milling and pre-sintering. Fig. 2 is an SEM image of pre-sintered powder particles, and it can be seen from fig. 2 that the powders are uniformly dispersed and bridged with each other.
S4, sintering: placing the presintered powder in a vacuum sintering furnace, and vacuumizing to 9 ╳ 10 -3 Pa, heating to 1050 ℃ at a speed of 8 ℃/min, preserving heat for sintering, stopping heating after sintering for 3 hours, cooling, and taking out to obtain sintered powder.
S5, crushing: ball milling and crushing are carried out on the sintered powder, a polyurethane ball milling tank and stainless steel grinding balls are adopted for ball milling, and the weight ratio of ball materials is 6: and 1, wet milling is carried out by taking absolute ethyl alcohol as a solvent, the volume ratio of the materials to the milling balls to the absolute ethyl alcohol is 1:1.2, the ball milling rotating speed is 200rpm, and after ball milling is carried out for 6 hours, the materials are taken out and dried, so that the W-B powder material is obtained. FIG. 3 shows XR of the prepared W-B powder materialIn the D diagram, only single-phase WB phase is detected in the diagram 3, and other phases are not detected, which indicates that the prepared W-B powder material is pure-phase WB powder material. Fig. 4 is an SEM image of WB powder material, and it can be seen from fig. 4 that WB powder material particles are fine and uniform. The particle size of the WB powder material was measured by a laser particle sizer, and the average particle size (D50) of the powder material was 1.93 μm. The real density of the WB powder material is tested by adopting a real density analyzer, and the real density of the powder material is 15.6g/cm 3 99.4% of the theoretical density of WB.
Example 2
Example 2 differs from example 1 in that in step S1, W powder and B powder are weighed as raw material powders according to an atomic weight ratio W: b=2:1.2, and in step S4, the temperature is raised to 1150 ℃ and the heat is preserved for sintering for 3 hours, and the other preparation steps are the same as in example 1, so that a W-B powder material is prepared.
FIG. 5 is an XRD pattern of the W-B powder material prepared in example 2, in which only single phase W is detected in FIG. 5 2 The phase B does not detect other phases, which indicates that the prepared W-B powder material is pure phase W 2 And B, powder material. FIG. 6 is W 2 B SEM image of powder material, from FIG. 6, it can be seen that W 2 The particles of the powder material B are fine and uniform. Testing W with laser particle sizer 2 The particle diameter of the powder material was measured and found to be 2.18. Mu.m, which is the average particle diameter (D50). Testing W by using true density analyzer 2 B the true density of the powder material is 16.9g/cm 3 Is W 2 B98.9% of theoretical density.
Example 3
Example 3 differs from example 2 in that in step S1, W powder and B powder are weighed as raw material powders in an atomic ratio W: b=2:5, and the remaining preparation steps are the same as in example 2, to prepare a W-B powder material.
FIG. 7 is an XRD pattern of the W-B powder material prepared in example 3, in which only single phase W is detected in FIG. 7 2 B 5 The phase, other phases are not detected, which indicates that the prepared W-B powder material is pure phase W 2 B 5 Powder material.
FIG. 8 is W 2 B 5 From the SEM image of the powder material, it can be seen from FIG. 8 that W 2 B 5 The powder material has fine and uniform particles. Testing W with laser particle sizer 2 B 5 The particle diameter of the powder material was found to be 1.43 μm in average particle diameter (D50). Testing W by using true density analyzer 2 B 5 The true density of the powder material is 11.1g/cm 3 Is W 2 B 5 99.3% of theoretical density.
Example 4
Example 4 differs from example 2 in that in step S1, the ratio of the average particle diameters of W powder and B powder in the raw material powder is 2 μm:10 μm, and the other preparation steps were the same as in example 2, to obtain a W-B powder material.
FIG. 9 is an XRD pattern of the W-B powder material prepared in example 4, in which only single-phase W was detected 2 The phase B does not detect other phases, which indicates that the prepared W-B powder material is pure phase W 2 And B, powder material. FIG. 10 is W 2 B SEM image of powder material, from FIG. 10, it can be seen that W 2 The particles of the powder material B are fine and uniform. Testing W with laser particle sizer 2 The particle diameter of the powder material was measured to be 3.26. Mu.m, which is the average particle diameter (D50). Testing W by using true density analyzer 2 B the true density of the powder material is 16.95g/cm 3 Is W 2 B99.2% of theoretical density.
Example 5
Example 5 differs from example 4 in that in step S1, 1% polyethylene glycol is weighed in terms of the mass percentage of the raw material powder, and the other preparation steps are the same as in example 4, to prepare a W-B-based powder material.
FIG. 11 is an XRD pattern of the W-B powder material prepared in example 5, in which only single-phase W was detected 2 The phase B does not detect other phases, which indicates that the prepared W-B powder material is pure phase W 2 And B, powder material. Detection of W 2 Microstructure of B powder material, W obtained 2 The particles of the powder material B are fine and uniform. Testing W with laser particle sizer 2 The particle diameter of the powder material was measured to be 3.36 μm in average particle diameter (D50). Testing W by using true density analyzer 2 B the true density of the powder material is 16.92g/cm 3 Is W 2 B99% of theoretical density.
Comparative example 1
Comparative example 1 was different from example 4 in that the ball milling in step S2 was omitted, and the other preparation steps were the same as in example 4, to prepare a W-B-based powder material.
FIG. 12 is an XRD pattern of the W-B system powder material prepared in comparative example 1, except that W was detected 2 Phase B, also WB phase was detected. As can be seen from a combination of example 4 and comparative example 1, ball milling helps promote the W-B solid phase reaction to form pure phase W 2 The main reason for analysis is that after ball milling, the W powder and the B powder are subjected to surface activation, have higher surface energy, promote the interdiffusion of W atoms and B atoms in the sintering process, and further prepare pure phase W 2 And B, powder material.
Comparative example 2
Comparative example 2 was different from example 4 in that polyethylene glycol was not added in step S1, and the other preparation steps were the same as in example 4, to obtain a W-B-based powder material.
FIG. 13 is an XRD pattern of a W-B powder material prepared in comparative example 2, except that W was detected 2 Phase B, also WB phase was detected. As can be seen from the combination of example 4 and comparative example 2, the addition of polyethylene glycol during ball milling helps promote the solid phase reaction of W-B to form pure phase W 2 The main reason for analysis is that polyethylene glycol can play a bridging role between W powder and B powder in the ball milling process, and realize mechanical interlocking between the W powder and the B powder under the ball milling effect, thereby shortening the diffusion path between W atom and B atom in the sintering process, promoting the mutual diffusion of the W atom and the B atom in the sintering process, and further preparing the pure phase W 2 And B, powder material.
Comparative example 3
Comparative example 3 differs from example 4 in that in step S1, 0.5% of polyethylene glycol was weighed in terms of the mass percentage of the raw material powder, and the remaining preparation steps were the same as in example 4, to prepare a W-B-based powder material.
FIG. 14 is an XRD pattern of a W-B powder material prepared in comparative example 3, except that W was detected 2 Phase B, also a small amount of WB phase was detected. It is apparent from the combination of example 4 and comparative example 3 that the amount of polyethylene glycol added during the ball milling was too small, the bridging effect between the W powder and the B powder was reduced, the promotion effect of the subsequent sintering diffusion of the W powder and the B powder was reduced, and a small amount of WB phase was also present.
Comparative example 4
Comparative example 4 is different from example 4 in that in step S1, the average molecular weight of polyethylene glycol is 4000 (PEG 4000, CAS 25322-68-3), and the other preparation steps are the same as in example 4, to prepare a W-B-based powder material.
FIG. 15 is an XRD pattern of the W-B powder material prepared in comparative example 4, except that W was detected 2 Phase B, also a small amount of WB phase was detected. In combination with example 4 and comparative example 4, it is understood that the molecular weight of polyethylene glycol has a direct influence on bridging between W powder and B powder, that the molecular weight of polyethylene glycol is too small, and that the bridging between W powder and B powder of polyethylene glycol is reduced.
Comparative example 5
Comparative example 5 differs from example 3 in that in step S4, sintering is performed by heating to 1150 ℃ and maintaining the temperature for 1 hour, and the other preparation steps are the same as in example 3, to prepare a W-B-based powder material.
FIG. 16 is an XRD pattern of the W-B system powder material prepared in comparative example 5, except that W was detected 2 B 5 Phase, also detect a small amount of W 2 And phase B. In combination with example 3 and comparative example 5, it was found that too short a sintering time was detrimental to the mutual sufficient diffusion between the atoms of the W powder and the B powder.
Comparative example 6
Comparative example 6 is different from example 2 in that in step S1, the ratio of the average particle diameters of W powder and B powder in the raw material powder is 40 μm:5 μm, and the other preparation steps were the same as in example 2, to obtain a W-B powder material.
FIG. 17 is an XRD pattern of the W-B system powder material prepared in comparative example 6, except thatWB phase was detected, and a small amount of W was also detected 2 B. As can be seen from the combination of example 2 and comparative example 6, the particle sizes of the W powder and the B powder are not matched, which is not favorable for the uniform dispersion of the W powder and the B powder in the ball milling process, and is also unfavorable for the bridging effect of polyethylene glycol in the ball milling process, so that the interdiffusion between W and B atoms is insufficient in the sintering process, and even if the raw material powder has the atomic metering ratio W: B=2:1.2, the preparation of comparative example 6 is mainly a WB phase, W 2 Phase B is rare.
Comparative example 7
Comparative example 7 was different from example 1 in that in step S4, sintering was performed by heating to 950 ℃ and maintaining the temperature, and the other preparation steps were the same as in example 1, to obtain a W-B-based powder material.
FIG. 18 is an XRD pattern of the W-B powder material obtained by sintering at 1050℃in example 1 and sintering at 950℃in comparative example 7. As can be seen from FIG. 18, in comparative example 7, sintering at 950℃for 3 hours in step S4, a large amount of W phase was detected in the W-B powder material, indicating that sintering temperature was too low, W powder and B powder were insufficiently reacted, sintering at 1050℃for 3 hours in step S4 in example 1, the diffusion capacity of W atom and B atom was enhanced, facilitating the solid phase reaction, and further obtaining pure phase WB phase powder.
Comparative example 8
Comparative example 8 was different from example 2 in that in step S4, sintering was performed by heating to 1000 ℃ and maintaining the temperature for 3 hours, and the other preparation steps were the same as in example 1, to prepare a W-B-based powder material.
FIG. 19 is an XRD pattern of a W-B powder material obtained by sintering at 1150℃and 1000℃in comparative example 8, in which W was detected in the W-B powder material obtained by sintering at 1000℃in step S4 in comparative example 8, as can be seen from FIG. 19 2 B, the W phase and the WB phase were detected, which indicates that the solid phase sintering reaction temperature was too low, the reaction of the W powder and the B powder was insufficient, the sintering was performed at 1150℃for 3 hours in step S4 in example 2, the temperature was increased, the reaction ability and the diffusion ability were enhanced, and pure phase W was obtained 2 B phase powder.
The above embodiments are not intended to limit the scope of the present invention, so: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.

Claims (10)

1. The preparation method of the W-B powder material is characterized by comprising the following preparation steps:
s1, proportioning: weighing W powder and B powder according to a proportion as raw material powder, wherein the average particle size ratio of the W powder to the B powder in the raw material powder is 0.1-35 mu m: 0.1-30 mu m, weighing 1-3% of polyethylene glycol according to the mass percentage of the raw material powder, wherein the average molecular weight of the polyethylene glycol is 6000-12000;
s2, ball milling: ball milling and mixing the raw material powder and polyethylene glycol, and uniformly mixing to obtain mixed powder;
s3, presintering: the mixed powder is placed under the temperature condition of 250 ℃ to 650 ℃ for heat treatment for 1 to 8 hours, and presintered powder is obtained;
s4, sintering: sintering the presintered powder for 2-5 hours at the temperature of 1000-1200 ℃ to obtain sintered powder;
s5, crushing: and crushing the sintered powder to obtain the W-B powder material.
2. The method for producing a W-B powder material according to claim 1, wherein in step S1, W powder and B powder are weighed as raw material powders in an atomic ratio W.sub.1 (0.5 to 2.7).
3. The method for producing a W-B powder material according to claim 1, wherein in step S2, wet milling is performed, and the ball-to-material ratio of the wet milling is 2 to 10:1, the ball milling rotating speed is 100-500 rpm, and the ball milling time is 5-30 h.
4. The method for producing a W-B powder material according to claim 1, wherein in step S1, W powder and B powder are weighed as raw material powders in an atomic ratio W.sub.B=1 (1 to 1.2).
5. The method of producing a W-B powder material according to claim 4, wherein in step S4, the pre-sintered powder is sintered at a temperature of 1000 to 1100 ℃ for 2 to 5 hours to obtain a sintered powder.
6. The method for producing a W-B powder material according to claim 1, wherein in step S1, W powder and B powder are weighed as raw material powders in an atomic ratio W.sub.2 (5 to 5.3).
7. The method for producing a W-B powder material according to claim 1, wherein in step S1, W powder and B powder are weighed as raw material powders in an atomic ratio W.sub.2 (1.1 to 1.3).
8. The method of producing a W-B powder material according to claim 6 or 7, wherein in step S4, the pre-sintered powder is sintered at a temperature of 1100 to 1200 ℃ for 2 to 5 hours to obtain a sintered powder.
9. A W-B-based powder material obtained by the method for producing a W-B-based powder material according to any one of claims 1 to 8.
10. The W-B powder material according to claim 9, wherein the W-B powder material has a phase structure of WB phase and W phase 2 B phase or W 2 B 5 One of the phases.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005263503A (en) * 2004-03-16 2005-09-29 Akita Prefecture W(c, n)-wb-based compound material and its forming process
CN116199229A (en) * 2022-09-30 2023-06-02 崇义章源钨业股份有限公司 High-fluidity pure-phase tungsten diboride and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005263503A (en) * 2004-03-16 2005-09-29 Akita Prefecture W(c, n)-wb-based compound material and its forming process
CN116199229A (en) * 2022-09-30 2023-06-02 崇义章源钨业股份有限公司 High-fluidity pure-phase tungsten diboride and preparation method thereof

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